Allium chemistry: Microwave spectroscopic identification, mechanism of formation, synthesis, and reactions of (E,Z)-Propanethial S-oxide, the lachrymatory factor of the onion (Allium cepa)

被引:58
作者
Block, E
Gillies, JZ
Gillies, CW
Bazzi, AA
Putman, D
Revelle, LK
Wang, DY
Zhang, X
机构
[1] SIENA COLL, DEPT CHEM, LOUDONVILLE, NY 12211 USA
[2] RENSSELAER POLYTECH INST, DEPT CHEM, TROY, NY 12180 USA
[3] UNIV MISSOURI, ST LOUIS, MO 63121 USA
关键词
D O I
10.1021/ja960722j
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Flow pyrolysis of 2-methyl-2-propyl 1'-propenyl sulfoxide (9b) affords a 98:2 mixture of (Z)- and (E)-propanethial S-oxide ((Z)- and (E)-5b), both characterized by Fourier transform microwave (FT-MW) spectroscopy, Sulfines (Z)- and (E)-5b are also identified by FT-MW in chopped onion volatiles and by NMR spectroscopy in onion extracts. Similarly, flow pyrolysis of 2-methyl-2-propyl vinyl sulfoxide (9c) affords (Z)- and (E)-isomers of ethanethial S-oxide (5a), identified by FT-MW methods. Pyrolysis in the presence of D2O affords (Z)-5a-d(1) and (Z)-5a-d(2) from 99 and (Z)-5b-d(1) from 9b; (Z)-5b-d(1) is also produced when an onion is homogenized in D2O. Pyrolysis of 9c with ethyl propiolate gives ethyl (E)-3-(vinylsulfinyl)acrylate (10). Neat 59 at 100 degrees C gives acetaldehyde. On standing, 5b dimerizes to trans-3,3-diethyl-1,2-dithietane 1,1-dioxide (12a); Me(3)SiCH=S+-O- (5f) undergoes an analogous dimerization. Compound 5b shows moderate potency as an anticarcinogen in inducing the enzyme quinone reductase.
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页码:7492 / 7501
页数:10
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